CN104252973A - Color-changing fibriform supercapacitor and preparation method thereof - Google Patents

Color-changing fibriform supercapacitor and preparation method thereof Download PDF

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CN104252973A
CN104252973A CN201410448642.8A CN201410448642A CN104252973A CN 104252973 A CN104252973 A CN 104252973A CN 201410448642 A CN201410448642 A CN 201410448642A CN 104252973 A CN104252973 A CN 104252973A
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carbon nano
ultracapacitor
polyaniline
tube film
fibrous
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CN104252973B (en
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彭慧胜
陈旭丽
林惠娟
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Fudan University
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    • Y02E60/13Energy storage using capacitors

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Abstract

The invention belongs to the technical field of knittable intelligent power storage devices, in particular to a color-changing fibriform supercapacitor and a preparation method thereof. The preparation method comprises the following steps: firstly, winding one layer of carbon nano tube film on elastic rubber fibers to form a fibriform elastic electric conduction electrode; erasing a middle section of the carbon nano tube film to disconnect the carbon nano tube film; respectively taking two sides as electrodes, and coating one layer of polyaniline by electrodeposition on two elastic electrodes; coating one layer of polyvinyl alcohol/ phosphoric acid gel electrolyte on two polyaniline/ carbon nano tube composite electrodes and a notch between the two electrodes to obtain the intelligent fibriform supercapacitor. The supercapacitor has good knittability and can change colors along with different voltages of two poles, so that different energy storage states can be displayed through color state, meanwhile, different patterns can be formed by weaving, the supercapacitor can be used as a display device while being used as the energy storage device, and therefore the supercapacitor has a good application prospect.

Description

Fibrous ultracapacitor of a kind of changeable colour and preparation method thereof
Technical field
The invention belongs to and can weave energy storage device technical field, fibrous ultracapacitor being specifically related to a kind of intelligence and preparation method thereof and application.
Background technology
In recent years, smart electronics product becomes the mainstream development direction of electronic product gradually, various concept product proposes in succession, the intelligent glasses etc. of the smart phone of such as Samsung, the intelligent wristwatch of NIKE, Google, represent the forward position in this field, also bring great convenience for our high-quality life in future. [1-8]meanwhile, we also need to develop corresponding energy storage device, energy supply for it, and such as ultracapacitor occupies critical role because having higher power density, specific capacity and energy density in energy storage device. [9]imagination ultracapacitor changes intuitively if in use can show certain along with the change of energy storage state, so user just can fast, the energy storage state of monitoring devices in real time, so that precognition in time charging before depleted of energy, thus provide safeguard for the safe and highly efficient operation of device.Electrochromic material be a kind of can the material of variable color under certain voltage or the function of current, utilize this characteristic of electrochromic material to be expected to realize the intellectuality of ultracapacitor.Recently, have indivedual report to carry out Primary Study to the discoloration of electrochromic material and energy-storage property, but complete intelligent ultracapacitor is still unrealized. [10-13]
On the other hand, wearable mobile electronic device becomes one of mainstream development direction of society electronic device, is expected to be popularized in our future life, and therefore we need the energy supply for it of the corresponding energy-storage system of development badly. [6,14-18]for addressing this problem, fibrous ultracapacitor obtain recently extensively research for the preparation of can weave, wearable energy storage device. [19-26]compared with traditional plane ultracapacitor, fibrous ultracapacitor has can be woven into the special performance such as energy storage fabric or implantation clothes.Recently, large quantity research is had to be devoted to development new material, optimization material or device architecture to improve the electrochemical energy storage performance of fibrous ultracapacitor, but up to the present still need badly and give fibrous intelligent ultracapacitor more function, multi-functional is the main flow direction of the development of current wearable portable minisize electronics.
Summary of the invention
The object of the present invention is to provide a kind of threadiness, can occur fast with energy storage state, the intelligent ultracapacitor of reversible color change and preparation method thereof.
Ultracapacitor provided by the invention, the material obtained on elastic caoutchouc fiber by carbon nano-tube (CNT) thinfilms of super in-line arrangement is as stretching conductive substrates, electrochromic polyaniline (PANI) can be there is by electrochemical deposition method) on the carbon nano-tube film that is deposited on super in-line arrangement and the Polymerization of Polyaniline/carbon Nanotube composite material obtained as electrode, by polyvinyl alcohol/phosphoric acid composite (PVA/H 3pO 4) as gel electrolyte; This ultracapacitor is threadiness, changeable colour, can be woven into fabric, for display.As shown in Figure 1.
The preparation method of threadiness provided by the invention, changeable colour ultracapacitor, its concrete steps are:
(1) by elastic caoutchouc fiber with 100% amount of tension stretch;
(2) on the elastic caoutchouc fiber being in extended state, the carbon nano-tube film of super in-line arrangement is wound around, as conductive substrates; This carbon nano-tube film can pull out by spinning in carbon nano pipe array, and the spun carbon nano pipe array wherein used is prepared by chemical vapour deposition technique;
(3) remove pulling force and make the former length of elastic caoutchouc fiber recovery, at its two ends copper cash from extraction electrode line carbon nano-tube film;
(4) carbon nano-tube film of the position with two copper cash same distance is wiped (namely wiping at the carbon nano-tube film of one section, the centre of conductive substrates), wiping the matrix of both sides respectively as two electrodes of carbon nano-tube film position;
(5) by electrochemical deposition method, at the upper equal potentiostatic electrodeposition polyaniline of two sections of carbon nano-tube films (i.e. two electrode matrixs), two sections of Polymerization of Polyaniline/carbon Nanotube composite materials are obtained, as positive and negative two electrodes;
(6) on Polymerization of Polyaniline/carbon Nanotube composite material, be all coated with layer of polyethylene alcohol/phosphoric acid gel-like electrolyte with middle gap of wiping carbon nano-tube film, namely obtain the ultracapacitor of threadiness, changeable colour.
In the present invention, the quality of described electro-deposition polyaniline shifts calculating by Faraday's law by the electricity occurred in electrodeposition process, in Polymerization of Polyaniline/carbon Nanotube composite material, the mass content of PANI is 20% ~ 90%, and the mass content of preferred PANI is 40% ~ 80%; With the mass content of PANI be 70% energy storage and variable color resultant effect best.
In the present invention, the thickness being wrapped in the carbon nano-tube film on elastic caoutchouc fiber is 20 ~ 100 nm, and preferred thickness is 20 ~ 60 nm.
Ultracapacitor of the present invention, in charge and discharge process can there is variable color in both positive and negative polarity respectively, and different color state has reacted different energy storage states.Such as shown in Figure 3, positive pole is at 1 V, 0.5 V and 0 V and show blueness, green and faint yellow respectively below, and due to the symmetrical structure of this ultracapacitor, vice versa in negative pole variable color.
Ultracapacitor of the present invention, is combined into various pattern by braiding, in charge and discharge process, and positive and negative polarities variable color with the difference of residing voltage of each intelligent ultracapacitor, thus this fabric as display device, can show different patterns.
In fibrous ultracapacitor prepared by the present invention, polyaniline content is that the specific capacity of the Polymerization of Polyaniline/carbon Nanotube composite material of 70% can reach 255.5 F/g (0.19 mF/cm) under the current density of 1 A/g, and energy density and power density can reach 12.75 Wh/kg and 1493.6 W/kg respectively; And this ultracapacitor has good flexibility and tensility, bending through 1000 times or can keep the specific capacity of more than 97% under the amount of tension with 100% stretches, after multi-drawing, specific capacity is substantially constant.
The present invention adopt scanning electron microscopy (SEM) to aligned carbon nanotube and and the combined electrode structure of polyaniline characterize.As shown in Figure 4, the even carbon nanotube on elastomer surface distributes and arrangement high-sequential, provides the foundation for combination electrode has good conductivity.Fig. 5 shows, after the carbon nano-tube substrates polyaniline of orientation, whole fiber electrode still keeps even, orderly helical structure, as Fig. 5 b shows after further amplification, the polyaniline on carbon nano-tube film surface is dispersed, the phenomenon such as soilless sticking, caking, this just effectively ensure that effective performance of its energy-storage property and the stability in thermal energy storage process.
For obtaining the ultracapacitor with good energy-storage property, the present invention explores polyaniline content different in combination electrode to the impact of ultracapacitor energy storage performance.As shown in Figure 6, to sweep the cyclic voltammetry curve under speed at 10 mV/s for the ultracapacitor of different polyaniline content.Can find out, be increased in 70% process at polyaniline content by 20%, redox peak intensity increases with the increase of polyaniline content, when polyaniline content increases to 90% by 70% further, peak shape broadens weakened, and this reunites due to polyaniline that carbon nano tube surface is blocked up with causing caused by resistance increases.In addition, it can also be seen that the variation tendency of specific capacity from this cyclic voltammogram, tentatively infer that the sample specific capacity of in certain current density range 70% is higher.
The present invention has carried out constant current charge-discharge test to the ultracapacitor of different polyaniline content under 1 A/g, and test curve as shown in Figure 7.Can find out, when polyaniline content increases to 70% by 20%, the voltage drop U=IR on discharge curve is increased to 0.087 V by 0.065 V, change very little, illustrate that internal resistance change is very little, and discharge time is elongated, illustrates that electrode discharge specific capacity increases with the increase of polyaniline content; And when this content increases to 90% further, it is 0.298 V that voltage drop U=IR on discharge curve is increased sharply by 0.087 V, shorten discharge time, namely specific capacity reduces simultaneously, and to be that the polyaniline piled up due to carbon nano tube surface is blocked up cause caused by electrode material internal resistance increases for this.
For the specific capacity Changing Pattern of sample under different current density of characterized systematically different polyaniline content, we to each capacitor 1, 3, 5, 8, constant current charge-discharge test has been carried out respectively under 10 A/g, as shown in Figure 8, can find out, similar to the Changing Pattern in plane ultracapacitor, constant current charge-discharge is carried out under the current density of 1 A/g, polyaniline content is 20%, 50%, 70%, the electrode of super capacitor specific capacity of 90% is respectively 82.2, 209.1, 255.5, 188.9 F/g, namely when polyaniline content is lower, electrode specific capacity increases with the increase of polyaniline content, but the sample that content is 90% effectively cannot contact with carbon nano-tube (Fig. 9) due to the polyaniline that carbon nano tube surface is blocked up, cause ion transfer efficiency step-down, internal resistance increases, thus cause specific capacity to reduce, this point as can be seen from the voltage drop U=IR in above-mentioned Fig. 7 also.Polyaniline content be 70% the energy density of ultracapacitor prepared of combination electrode and power density under the current density of 1 A/g and 10 A/g, be calculated as 12.75 Wh/g and 1493.6 W/kg respectively.
Equally, the present invention has also investigated the impact of different-thickness carbon nano-tube film on electrode specific capacity, as shown in Figure 10, can find out, be increased in 100 nm processes at carbon nano-tube film thickness by 20 nm, specific capacity under 1 A/g and 10 A/g increases to 327.4 F/g and 188.4 F/g by 255.5 F/g and 74.1 F/g respectively, this is because the increase of the carbon nano-tube number of plies is conducive to reducing caused by electrode resistance, consider light transmission, the factor such as preparation process and cost, the present invention chooses ultracapacitor based on the thick carbon nano-tube of 20 nm as main study subject.
Comprehensive above discussion, the present invention chooses ultracapacitor prepared by polyaniline content is 70%, carbon nano-tube thickness is 20 nm combination electrode as main study subject, and by differently sweeping the lower cyclic voltammetry of speed, constant current charge-discharge under different current density tests and long-acting loop test and electrochemical impedance spectroscopy test the high rate performance and the cyclical stability that characterize device.As shown in figure 11, this ultracapacitor is when sweeping speed and increasing to 50 mV/s by 10 mV/s, redox peak broadens, but can not disappear, illustrate in this fibrous electrode of super capacitor charge and discharge process and Quick Oxidation reduction reaction can occur, constant current charge-discharge curve as shown in Figure 12 under different current density can find out that each curve all has good symmetry, illustrate that this ultracapacitor has higher coulombic efficiency, and the shape of curve can keep well, illustrate that this ultracapacitor has good high rate performance.In addition, for characterizing its long-acting cycle performance, we carry out long-acting loop test to this ultracapacitor under 1 A/g, test result as shown in figure 13, can find out that this ultracapacitor capacity in initial 500 circle circulations declines obvious, drop to 82.9% of initial capacity, decline here causes caused by bath resistance increase because this fibrous ultracapacitor electrolysis matter becomes dry further, and this point can be proved by the electrochemical impedance spectroscopy test result in Figure 14 [27]namely the increase that its Nyquist composes intercept illustrates that this bath resistance increases, simultaneously, this Nyquist spectral shape is substantially constant, and its low frequency part still keeps the inclination angle close to 90 °, illustrates that this device energy storage is still typical capacitance behavior, and as can be seen from Figure 13, this ultracapacitor is specific capacity kept stable in 9500 circle circulations below, after 10000 circle circulations, can keep 69.1% of its initial capacity.
Because fibrous electrodes adopts elastic caoutchouc as substrate, surperficial Polymerization of Polyaniline/carbon Nanotube compound has the helical structure of height in-line arrangement, therefore this electrode have good flexible, the performance such as can stretch.The present invention has investigated this fibrous ultracapacitor electrochemical energy storage performance bending, stability in drawing process, be the curve that this capacity of super capacitor changes with angle of bend as shown in figure 15, can find out, the capacity of this ultracapacitor increases to 180 ° with angle of bend by 0 °, its volume change is no more than 0.6%, to its carry out angle of bend be 180 ° folding with unfold back and forth, can see that this ultracapacitor is when diastole state and folded state, its capacity is substantially equal, and after nearly 1000 circles circulate, capacity can keep 93.46%(Figure 16).Subsequently, we have investigated again the impact of this capacity of super capacitor Tensile, be the change of this capacity of super capacitor with percentage elongation as shown in figure 17, can find out, when its percentage elongation is increased to 100% by 0%, its volume change is no more than 2.96%, after removing this pulling force, its capacity gos up by a small margin for 97.46% of original value, and stretches 100 times with the percentage elongation of 100%, and its capacity still can keep 97.88%(Figure 18 of initial value).Therefore, as can be seen from the above results, this ultracapacitor is in bending, drawing process, and its energy-storage property has good stability.In addition, this fibrous ultracapacitor also has good flexibility and braiding property, as shown in figure 19, this fibrous ultracapacitor can carry out arbitrarily bending knotting as common cotton rope, then show shown in Figure 20 that this fibrous ultracapacitor can be woven into textile-like capacitor, and can lightening LED lamp after two fabric capacitor devices are connected.Illustrate thus, this fibrous ultracapacitor independently can be prepared into fabric or implant in the fabric such as ordinary clothing, bag and form wearable ultracapacitor, is the energy supplies such as light-emitting diode display, wrist-watch, heart rate monitor, hearing aids.
This fibrous ultracapacitor except having above good electrochemical energy storage and excellent flexibility, can stretch, except stitchability, the more important thing is that this fibrous ultracapacitor is in charge and discharge process, both positive and negative polarity can variable color along with the difference of voltage residing for it, thus shows the energy storage state of himself in real time, intuitively.Be photo that the color in this fibrous ultracapacitor charge and discharge process changes with voltage as shown in figure 21, can find out, when this fibrous ultracapacitor voltage be-1 ,-0.5,0,0.5,1 V time, negative pole is respectively blueness, green, light green, faint yellow, lark, on the contrary, positive pole is respectively lark, faint yellow, light green, green, blueness, and the mechanism of variable color is because polyaniline in charge and discharge process, under certain voltage, electrochemical redox reaction occurs [28-30], at 1 V of 100% charging complete, positive pole is in oxidized state , be presented as blueness, negative pole is in full reduction-state , be presented as faint yellow; When both end voltage is 0.5 V, positive pole is in partial oxidation state , be presented as green, negative pole is still in full reduction-state, it is faint yellow to be presented as; When two pole tensions are 0 V, in the two poles of the earth, polyaniline all has a small part oxidized and is in light green, and when two voltage across poles are negative value, vice versa.Therefore, can judge voltage status residing for it and energy storage state by electrode color state, namely this ultracapacitor shows good intelligent color-changing.
For investigating the invertibity of this fibrous ultracapacitor intelligent color-changing ability, we observe its discoloration after carrying out 3000 long-acting circulations of constant current charge-discharge, as shown in figure 22, be respectively the photo of threadiness arranged in parallel for the both positive and negative polarity of fibrous ultracapacitor intelligence ultracapacitor after 3000 charge and discharge cycles when 0 V and 1 V, can find out, color change still clearly, can intuitively indicate its energy storage state, illustrate that the useful life of this fibrous intelligent ultracapacitor is longer.
Based on stitchability and unique intelligent color-changing of this fibrous intelligent ultracapacitor excellence, the electrode of this fibrous intelligent ultracapacitor is woven into textile-like intelligence ultracapacitor as shown in fig. 23 a by us, using its transverse fiber and longitudinal fiber as the positive pole of ultracapacitor and negative pole, discharge and recharge is carried out to it, then complete in electric discharge, namely, during-1 V, this textile-like ultracapacitor longitudinal fiber is presented as blueness (Figure 23 b), and transverse fiber is shown as faint yellow; On the contrary, when charging process completes, when namely condenser voltage is 1 V, this fabric ultracapacitor horizontal line is presented as blueness, and ordinate is presented as faint yellow (Figure 23 c).Based on the discoloration of each fiber in this textile-like intelligence ultracapacitor, can be used for the intelligent display to pattern, such as, using the horizontal line of centre and middle ordinate as a pole, all the other are as another pole, for display "+" as shown in Figure 23 d, in like manner, can show " F " and " H " as shown in Figure 23 e and f.Here just simple example illustrates, distributed by suitable electrode and be connected with circuit, this fabric can be used for showing other numeral, symbol, letter and patterns.Meanwhile, the intelligent ultracapacitor of threadiness provided by the present invention also can inweave in conventional fabrics easily, inweaves in cotton string gloves, show smiling face during charging complete by this fibrous intelligent ultracapacitor, shows face of crying when having discharged.In a word, distribute be connected with circuit by suitably braiding, electrode, this fibrous intelligent ultracapacitor can be similar to the pattern that the display of modernization digital display technique needs arbitrarily, the intelligent ultracapacitor fabric realizing carrying out colored intelligent display will be expected to by introducing other sensitive materials, this fabric integrates energy storage, intelligent and Presentation Function, is expected to be used widely.
In sum, the present invention has prepared a kind of fibrous ultracapacitor of changeable colour first, this ultracapacitor with IR fiber be elastic substrates, with the super in-line arrangement carbon nano-tube film be wrapped on elastic caoutchouc fiber be conducting base, with the polyaniline being electrochemically-deposited in carbon nano tube surface for ultracapacitor prepared by energy storage material, simultaneously due to the electrochromic property of polyaniline, this fibrous ultracapacitor both positive and negative polarity can the variable color with the change of voltage, thus has and react the intelligent of energy storage state residing for himself intuitively, in real time.In addition, this fibrous intelligent ultracapacitor has good flexibility and tensility, be 100% stretching 100 times through 1000 circles bending (angle is 180 °) or drawn amount, capacity all can keep more than 97%, and this fibrous ultracapacitor can be woven into fabric, there is good stitchability and wearable property.Utilize stitchability and the colourability of this fibrous ultracapacitor, several fibers shape ultracapacitor can be woven into fabric and show different shapes, utilize the discoloration in its charge and discharge process thus, can by this textile-like ultracapacitor be used as display device, make its as while energy storage device also as display device.
The method of the intelligent ultracapacitor of preparation provided by the invention, can expand to other electrochromism macromolecular materials from polyaniline, as polythiophene, polypyrrole etc., also can expand to electrochromic metal oxide, as WO 3, V 2o 5, MoO 5, TiO 2, IrO 2, Ir (OH) 2deng, for prepare the intelligent ultracapacitor of colourful threadiness and exploitation new while provide the effective way with universality as energy storage device and display device.
Accompanying drawing explanation
Fig. 1 is the structural scheme of mechanism that fibrous changeable colour ultracapacitor of the present invention is woven into fabric and Polymerization of Polyaniline/carbon Nanotube combination electrode.
Fig. 2 is fibrous supercapacitor structures schematic diagram of the present invention.
Fig. 3 is the schematic diagram of fibrous supercapacitor positive electrode variable color of the present invention.
Fig. 4 is the stereoscan photograph after elastic caoutchouc fiber being wound around super in-line arrangement carbon nano-tube film.Wherein, (a) and (b) are respectively low power and high power photo, and in (b), illustration is the photo amplified further.
Fig. 5 elastic caoutchouc fiber is wound around the stereoscan photograph of super in-line arrangement carbon nano-tube film also on the carbon nanotubes after electro-deposition polyaniline.Wherein, (a) and (b) are respectively low power and high power photo, and in (b), illustration is the photo amplified further.
Fig. 6 is the cyclic voltammetry curve of fibrous ultracapacitor under 10 mV/s sweep speed of different polyaniline content.
Fig. 7 is the constant current charge-discharge curve of fibrous ultracapacitor under 1 A/g current density of different polyaniline content.
Fig. 8 be in electrode of super capacitor of the present invention polyaniline content and charging and discharging currents density on the impact of electrode specific capacity.
Fig. 9 is that in Polymerization of Polyaniline/carbon Nanotube combination electrode, polyaniline content is the electrode stereoscan photograph of the ultracapacitor of 90%, and interior illustration is the photo amplified further.
Figure 10 be in electrode of super capacitor of the present invention carbon nano-tube film thickness and charging and discharging currents density on the impact of electrode specific capacity.
Figure 11 to be polyaniline content be 70% the cyclic voltammetry curve of ultracapacitor device under difference sweeps speed.
Figure 12 to be polyaniline content be 70% the charging and discharging curve of ultracapacitor device under different current density.
Figure 13 to be polyaniline content be 70% ultracapacitor device long-acting cycle performance of constant current charge-discharge under 1 A/g, C 0the capacity before and after circulation is represented respectively with C.
Figure 14 is the electrochemical impedance spectroscopy before ultracapacitor of the present invention circulation and under 1 A/g after the circulation of constant current charge-discharge 3000 circle.
Figure 15 is the change of fibrous capacity of super capacitor of the present invention with angle of bend.C 0the capacity of bending front and back is represented respectively with C.
Figure 16 is the change of fibrous capacity of super capacitor of the present invention with number of bends.C 0the capacity of bending front and back is represented respectively with C.
Figure 17 is the change of fibrous capacity of super capacitor of the present invention with amount of tension.C 0the capacity before and after stretching is represented respectively with C.
Figure 18 is the change of fibrous capacity of super capacitor of the present invention with drawing numbers.C 0the capacity before and after stretching is represented respectively with C.
Figure 19 is the photo that fibrous ultracapacitor of the present invention carries out tiing a knot.
Figure 20 is that fibrous ultracapacitor of the present invention is woven into fabric and lights the photo of LED after being connected by two fabrics.
Figure 21 is the photo of fibrous ultracapacitor of the present invention variable color with change in voltage in charge and discharge process.
Figure 22 is the variable color photo of fibrous ultracapacitor of the present invention under the current density of 1 A/g after 3000 circle constant current charge-discharge circulations.
Figure 23 be textile-like of the present invention intelligence ultracapacitor at 0 V(a) ,-1 V(b), 1 V(c) time color state photo.Wherein, transverse fiber is positive pole, and longitudinal fiber is negative pole.This textile-like intelligence ultracapacitor is to the intelligent display photo of "+" (d), " F " (e), " H " (f).
Embodiment
Array can be spun by chemical vapor deposition for carbon nanotubes according to prior art [31], namely in a quartz tube furnace, be coated with the thick Al of 3 nm with surface 2o 3(there is one deck SiO on surface to the silicon chip of film and the thick Fe film of 1.2 nm 2film) as catalyst, with Ar/H 2gaseous mixture is carrier gas, with C 2h 2gas is carbon source, temperature is risen to 740 DEG C, carbon nano-tube starts growth, through the growth of 10-20 min, after obtaining the carbon nano pipe array of super in-line arrangement, from wherein pulling out super in-line arrangement carbon nano-tube film, be wrapped on the elastic caoutchouc fiber that is stretched, two ends copper cash extraction electrode, the a bit of carbon nano-tube film of intermediate erase, obtain the breach that about 1 mm is long, the carbon nano-tube film on both sides is disconnected, respectively as the two poles of the earth.
Polyaniline in combination electrode in carbon nano-tube is prepared by electrochemical polymerization method.Adopt three-electrode method, be respectively electrode and reference electrode with the Ag/AgCl electrode in Pt silk and KCl saturated aqueous solution, the mixed aqueous solution of 0.1 M and 1 M is respectively for electrolyte with aniline and sulfuric acid concentration, carbon nano-tube film connects work electrode, setting constant potential is that 0.75 V carries out potentiostatic electrodeposition, by Faraday's law, the electricity occurred in electrodeposition process is converted into the quality of deposition polyaniline, controls deposition electricity and make the mass fraction of polyaniline in gained combination electrode be respectively 20%, 50%, 70% and 90%. [32]
Comprise PVA/H 3pO 4the compound method of gel electrolyte is as follows, first spends the night swelling in deionized water for 1 g PVA, then is heated to 90 DEG C, stirring 2 h to dissolving, adding 1 g concentrated phosphoric acid (H after being cooled to room temperature 3pO 4mass fraction is 85 wt%), stir [33].
Changeable colour threadiness ultracapacitor assembling, above-mentioned preparation two copper line electrode lead-in wire between two ends PANI/CNT combination electrode on and two interelectrode breach all apply layer of polyethylene alcohol (PVA)/phosphoric acid (H 3pO 4) gel electrolyte, obtain changeable colour threadiness ultracapacitor thus.
The structure of combination electrode is characterized by scanning electron microscopy (Hitachi, FE-SEM S-4800 operated at 1 kV).Constant current charge-discharge test in electrochemical energy storage performance and long-acting loop test are by Arbin multi-channel electrochemical tester (Arbin, MSTAT-5 V/10 mA/16 Ch) carry out, cyclic voltammetry is undertaken by electrochemical workstation (CHI 660D).In tensile property test, the two poles of the earth of fibrous ultracapacitor are fixed on specimen holder, by HY0350 Table-top Universal Testing Instrument restrained stretching amount, the electrochemical energy storage performance in its drawing process of synchronism detection.Ultraviolet spectra is by UV-2550(Shimadzu) characterize.
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Claims (5)

1. the fibrous ultracapacitor of a changeable colour, it is characterized in that being wrapped in material that elastic caoutchouc fiber obtains as stretching conductive substrates by the carbon nano-tube film of super in-line arrangement, can to be occurred on carbon nano-tube film that electrochromic polyaniline is deposited on super in-line arrangement by electrochemical deposition method and the Polymerization of Polyaniline/carbon Nanotube composite material obtained as electrode, by polyvinyl alcohol/phosphoric acid composite gel as electrolyte; This ultracapacitor is threadiness, changeable colour.
2. the fibrous ultracapacitor of changeable colour according to claim 1, is characterized in that the thickness of the carbon nano-tube film be wrapped on elastic caoutchouc fiber is 20 ~ 100 nm.
3. the fibrous ultracapacitor of changeable colour according to claim 1 and 2, is characterized in that in Polymerization of Polyaniline/carbon Nanotube composite material, and the mass content of polyaniline is 20% ~ 90%.
4. the fibrous ultracapacitor of changeable colour according to claim 1 and 2, is characterized in that polyaniline replaces with electrochromism polyphosphazene polymer thiophene or polypyrrole, or replaces with electrochromic metal oxide WO 3, V 2o 5, MoO 5, TiO 2, IrO 2or Ir (OH) 2.
5. the preparation method of the fibrous ultracapacitor of changeable colour as described in one of claim 1-4, is characterized in that concrete steps are as follows:
(1) by elastic caoutchouc fiber with 100% amount of tension stretch;
(2) on the elastic caoutchouc fiber being in extended state, the carbon nano-tube film of super in-line arrangement is wound around, as conductive substrates; This carbon nano-tube film can pull out by spinning in carbon nano pipe array, and the spun carbon nano pipe array wherein used is prepared by chemical vapour deposition technique;
(3) remove pulling force and make the former length of elastic caoutchouc fiber recovery, at its two ends copper cash from extraction electrode line carbon nano-tube film;
(4) carbon nano-tube film of one section, the centre of conductive substrates is wiped, wiping the matrix of both sides respectively as two electrodes of carbon nano-tube film position;
(5) by electrochemical deposition method, all by potentiostatic electrodeposition polyaniline on two sections of carbon nano-tube films, two sections of Polymerization of Polyaniline/carbon Nanotube composite materials are obtained, as positive and negative two electrodes;
(6) on Polymerization of Polyaniline/carbon Nanotube composite material, be all coated with layer of polyethylene alcohol/phosphoric acid gel-like electrolyte with middle gap of wiping carbon nano-tube film, namely obtain the fibrous ultracapacitor of threadiness, changeable colour.
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